TW501937B - Process for recovering onium hydroxides from solutions containing onium compounds - Google Patents

Abstract

In one embodiment, the present invention relates to a process for recovering an onium hydroxide from a solution containing an onium compound, including contacting the solution with a cation exchange material so that at least a portion of onium cations from the onium compound are adsorbed by the cation exchange material; contacting an acid with the cation exchange material to elute an onium salt; charging the onium salt to an electrochemical cell containing at least three compartments, a cathode, an anode, and in order from the anode to the cathode, a bipolar membrane and a cation selective membrane, and passing a current through the cell whereby the onium hydroxide is regenerated; and recovering the onium hydroxide from the cell. In another embodiment, the present invention relates to a process for recovering an onium hydroxide from a solution containing an onium compound, including contacting the solution with a cation exchange material so that at least a portion of onium cations from the onium compound are adsorbed by the cation exchange material; contacting an acid with the cation exchange material to elute an onium salt; charging the onium salt to an electrochemical cell containing at least two compartments, a cathode, an anode, and an anion selective membrane therebetween, and passing a current through the cell whereby the onium hydroxide is regenerated; and recovering the onium hydroxide from the cell.

Description

93 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 ___ B7 V. Description of the Invention (/) TECHNICAL FIELD The present invention relates to a method for regenerating the hydroxide key from a solution containing a gun compound. In particular, the present invention relates to a method for regenerating hydroxide from a solution containing a hydroxide gun and / or gun salt using a cation exchange material and an electrochemical cell. BACKGROUND OF THE INVENTION Hydroxide guns, such as quaternary ammonium hydroxide-including tetramethylammonium hydroxide (TMAH) and tetraethylammonium hydroxide (TEAH)-have been known as strong organic bases. Tetraammonium hydroxide has been found to be used in a variety of applications, including for zeolite manufacturing and polymer manufacturing. Aqueous solutions of quaternary ammonium hydroxide, especially TMAH, have also been widely used as photoresists for printed circuit boards and microelectronic wafers as developers. For various reasons, it is desirable to minimize the total amount of developer used in the manufacture of printed circuit boards and microelectronic wafers. One of the ways to minimize the total amount of hydroxide developer is to reuse waste developer. Reusing the developer reduces the number of discards and reduces waste issues. Waste developer contains impurities, including ionic impurities and non-ionic impurities. Ionic impurities include various metal cations, such as sodium, potassium, zinc, nickel, aluminum, copper, and calcium; and anions, such as halides, nitrates, nitrites, carbonates, carboxylates, and sulfates. Non-ionic impurities include photoresist, surfactant 'amines and many other organic molecules. Waste developer also contains a relatively low concentration of hydroxide developer. Therefore, it is still necessary to effectively recycle the reusable hydroxide developer so that it can be reused to reduce the total amount of developer used in the manufacture of printed circuit boards and microelectronic wafers. U.S. Patent 4,714,530 (Hale et al.) Describes a method for preparing high-purity quaternary ammonium hydroxide, which uses a cation exchange membrane to separate __ 4 ____ This paper is sized to the Chinese National Standard (CNS) A4 specification (210X 297 mm) (Please read the precautions on the back before this page)-Binding 501937 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 ___B7__ V. Description of the invention (Υ) Catholyte compartment and anolyte Compartment battery. The method includes pouring an aqueous quaternary ammonium hydroxide solution into an anolyte compartment, adding water to a catholyte compartment, and passing a direct current through an electrolytic cell to generate a high-purity tetrahydroxide that is then recovered in the catholyte compartment. Grade ammonium. The '530 patent also describes an improvement that involves heating quaternary ammonium hydroxide before pouring the hydroxide into the anolyte compartment of the electrolytic cell. U.S. Patent 4,938,854 (Sharifian et al.) Also describes an electrolytic process for purifying quaternary ammonium hydroxide to reduce the potential halide content. Electrolytic cells can be divided into anolyte compartments and catholyte compartments using compartments (which can be anion- or cation-selective membranes). The cathode in the catholyte compartment includes zinc, cadmium, tin, lead, copper, or titanium, or an alloy thereof, mercury or amalgam. Japanese Laid-Open Patent No. 60-131985 (1985) (Takahashi et al.) Describes a method for manufacturing high-purity quaternary ammonium hydroxide in an electrolytic cell, which is divided into an anode chamber and a cathode chamber by a cation exchange film . The quaternary ammonium hydroxide solution containing impurities is poured into the anode chamber and the direct current is applied between the two electrodes after the water has been poured into the cathode chamber. Purified quaternary ammonium hydroxide was obtained from the cathode compartment. The purified quaternary ammonium hydroxide contains reduced amounts of alkali metals, earth metals, anions, and the like. U.S. patents 5,439,564 and 5,545,309 relate to a method for treating a waste liquid containing organic quaternary ammonium hydroxide, the method comprising contacting the waste liquid with a cation exchange material, extracting the organic quaternary ammonium cation from the cation exchange material, and The anode, cathode and cation exchange membrane are used to electrolyze the eluent in a two-chamber electrolytic cell. Organic quaternary ammonium hydroxide is obtained from the cathode compartment of an electrolytic cell. ___----—- § ----- This paper size applies to Chinese National Standard (CNS) A4 (210X 297 mm) (Please read the precautions on the back before this page)

1T line 3 9 1X ο A7 B7 V. Description of the invention () Abstract of the invention In a specific embodiment, the present invention relates to a method for recovering a hydroxide gun from a solution containing a compound, including exchanging the solution with a cation Material contact, so that at least a portion of the gun cations from the recording compound are adsorbed by the cation exchange material; contact the acid and the cation exchange material to extract the gun salt; pour the gun salt into a cell containing at least three compartments, a cathode and a The anode, in the order from anode to cathode, also includes a bipolar film and a cation-selective film, and an electric current flows through the battery to regenerate the electrochemical cell of the hydroxide gun; and the hydroxide gun is recovered from the battery. _ In another specific embodiment, the present invention relates to a method for recovering a hydroxide gun from a solution containing a key compound, which comprises contacting the solution with a cation exchange material such that at least a portion of the gun cations from the gun compound are removed Cation exchange material adsorption; contact the acid and cation exchange material to extract gun salt; pour the gun salt into a cell containing at least two compartments, a cathode and an anode, and an anion-selective film disposed therein, and the current flows through the battery An electrochemical cell through which a hydroxide gun is regenerated; and a hydroxide gun is recovered from the battery. In yet another embodiment, the present invention relates to a method for recovering quaternary ammonium hydroxide from a solution containing a quaternary ammonium compound, which comprises contacting the solution with a cation exchange material such that at least a portion of the quaternary ammonium compound comes from Parts of the quaternary ammonium cation are adsorbed by the cation exchange material; contact the inorganic acid and the cation exchange material to extract the quaternary ammonium salt; pour the quaternary ammonium salt into a cell containing at least four cells, a cathode and an anode, and The sequence from anode to cathode also includes a bipolar film, an anion-selective film and a cation-selective film, and an electric current flows through the battery to regenerate the quaternary ammonium hydroxide electrochemical cell; _____6___ This paper is also suitable for China National Standard (CNS) A4 Specification (210X 297 mm) (Please read the precautions on the back before this page) Threading · Printed by the Employee Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 501937 Printed by the Employee Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs ^ A7 B7 5. Description of the invention (+) and recovery of quaternary ammonium hydroxide from batteries. In yet another specific embodiment, the present invention relates to recovering tetramethylammonium hydroxide from a waste solution containing a tetramethylammonium compound, which comprises contacting the waste solution with a cation exchange resin so that it is derived from the tetramethylammonium compound At least a part of the tetramethylammonium cation is adsorbed by the resin; contacting the inorganic acid with the cation exchange resin to extract the tetramethylammonium salt; pouring the tetramethylammonium salt into a cell containing at least five compartments, a cathode, An anode, in order from anode to cathode, further comprising a first bipolar film, an anion-selective film, a cation-selective film, and a second bipolar film, and a current flows through the battery to regenerate tetramethyl hydroxide An electrochemical cell of ammonium; and recovery of tetramethylammonium hydroxide from the battery O As a result of the method of the present invention, a recovered hydroxide gun solution can be obtained, and the concentration and purity of the solution are increased. Recycling the used hydroxide gun solution not only saves costs, but also reduces the need to synthesize new hydroxide compound solutions and eliminates the associated expensive purification procedures and reduces the toxicity of waste solution effluents, which is good for the environment. Increased amounts of water can be recovered after the hydroxide gun is removed from the solution. In addition, it is not necessary to store large amounts of chemicals. The relatively high concentration and purity of the hydroxide gun obtained by the present invention can be effectively used for various applications requiring a hydroxide gun solution. Brief Description of the Drawings Fig. 1 is a general view of two compartmental electrochemical cells including a unit cell according to the present invention; Fig. 2 is a general view of three compartmental electrochemical cells according to the present invention;槪 _______7_ This paper size is applicable to China National Standard (CNS) A4 specification (210X 29 < 7 mm) (Please read the precautions on the back before this page)- Installation, 11 • Line 501937 A7 _B7______ 5. Description of the Invention (Γ) Figure 4 is a schematic view of another three-cell electrochemical cell of the present invention; Figure 5 is a schematic view of another four-cell electrochemical cell of the present invention View; FIG. 6 is a perspective view of another four-compartment electrochemical cell of the present invention; FIG. 7 is a perspective view of a five-compartment electrochemical cell of the present invention; FIG. 8 is another nine-compartment electrochemical cell of the present invention Holm view of an electrochemical cell. DESCRIPTION OF PREFERRED EMBODIMENTS According to the method of the present invention, the hydroxide gun is regenerated (produced, purified, or recovered) from a solution containing the hydroxide gun and / or gun salt. Here, the gun compound is a compound containing gun cations, such as hydroxide and gun salt. In a specific embodiment, the solution containing a gun compound is a waste solution containing hydroxide after a development process, particularly related to a printed circuit board and a microelectronic wafer manufacturing process. Due to these procedures, impurities enter and contaminate the solution. In other words, the solution containing the key compound may be a used waste solution. In another embodiment, the gun compound-containing solution is a gun salt waste solution after it has been used in a procedure. The solution or waste solution may contain other compounds, such as the impurities mentioned above and / or below, and / or gun salts corresponding to hydroxide guns. The gun compound containing solution processed by the method of the present invention printed by the employee's consumer cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs is a mixture containing an oxidizable liquid and about 0.01% to about 50% by weight of the gun compound. Contains various amounts of one or more unwanted impurities, such as halides, carbonates, formate, nitrate, citrate, sulfate and other anions, some cationic metals such as zinc and calcium, sodium, potassium, including and Some neutral species, such as photosensitive resist film, methanol, amine, etc. The oxidizable liquid may be a mixture of water 'water and an organic liquid, or an organic liquid. Organic liquids include alcohols such as methanol and ethanol, ethylene glycol and the like. ^ The paper size is applicable to China's national standard 4 (210 × 297 mm) " 1 ~ 3 9 11 A7 ____B7 V. Description of the invention (k) In a specific embodiment, the method of the present invention is useful for reducing ionicity and non-ionicity. The amount of impurities present in the gun compound solution, such as quaternary ammonium hydroxide, is effective, while producing a high-purity hydroxide gun. In another embodiment, the method of the present invention reduces the metal ion impurities and organic impurities in gun compounds, such as quaternary ammonium hydroxide solution, and produces a high-purity hydroxide gun. In yet another embodiment, the present invention can be used to prepare purified hydroxides, such as quaternary ammonium hydroxide quaternary scale and tritium hydroxide. The hydroxide gun can usually be characterized by the following formula: A (〇H) x (I) where A is the gun base and X is an integer representing the valence of A. Examples of gun bases include ammonium, rust and fluorenyl. In a specific embodiment, the oxidizing gun should be sufficiently soluble in a solvent, such as water, alcohol or other organic liquid, or a mixture thereof for effective recovery. The quaternary ammonium hydroxide and quaternary hydroxide scales can be characterized by the following formula: mmm — R2 +

I

R1-A-R3 〇H * (ID

I R4 where A is a nitrogen or phosphorus atom, R1, R2, R3 and R4 are each independently a radical containing 1 to about 20 carbon atoms, and a hydroxyalkyl or alkoxyalkane containing 2 to about 20 carbon atoms Group, or hydroxyaryl group or R1 and R2 together with A can form __ _ ___9_ The standard of this paper is applicable to China National Standard (CNS) A4 specification (210 X 297 mm) ---------- batch Clothing-(Please read the notes on the back before ipi this page), -ιτ Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs, Employee Consumer Cooperative, 501937 A7 V. Description of the invention (y ^^ heterocyclic group, provided that the heterocyclic group contains One C two A group, R3 is the second bond. R1 to R4 can be straight or branched, and specific examples of alkyl groups containing 1 to 20 carbon atoms include methyl, ethyl, propyl, butane , Pentyl, hexyl, heptyl, nonyl, decyl, isodecyl, dodecyl, tridecyl, cetyl and octadecyl. R1, R2, R3 and R4 octyl, Isooctyl can also be hydroxyalkyl, such as hydroxyethyl and various isomers of hydroxypropyl, hydroxybutyl, hydroxypentyl, etc. In a preferred embodiment, R1, R2, R3 and R4 Each independently for a package A radical of one to ten carbon atoms and a radical of two to three carbon atoms. Specific examples of alkoxy end groups include ethoxyethyl, butoxymethyl, butoxybutyl, and the like. Various Examples of aryl and hydroxyaryl include phenyl, fluorenyl, and equivalent groups, in which the benzene ring has been substituted with one or more hydroxyl groups. The quaternary hydroxide of chemical formula III which can be recovered or purified according to the method of the present invention is represented by formula III: R1-N-R3 OH * (HD I R4 (please read the precautions on the back first and then this page). It is printed by the Consumer Cooperative of the Intellectual Property Office of the Ministry of Economic Affairs. R1, R2, R3 and R4 each As defined in Chemical Formula II. In a preferred embodiment, r1, f ,; ^ and V are each a radical containing 1 to about $ carbon atoms and a radical containing 2 or 3 carbon atoms. According to The quaternary ammonium hydroxide purified by the method of the present invention is most commonly tetramethylammonium hydroxide (TMAH) __ 10 degree scale applicable to Chinese National Standard (CNS) A4 specifications (210X 297 mmΊ '" 3 9 11 ο A7 B7 5. Description of the invention (?) Or tetraethylammonium hydroxide (TEAH). Specific examples of these ammonium hydroxides Including tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, tetra-n-octylammonium hydroxide, methyltriethylammonium hydroxide, diethyl hydroxide Dimethylammonium hydroxide, methyltripropylammonium hydroxide, methyltributylammonium hydroxide, cetyltrimethylammonium hydroxide, trimethylhydroxyethylammonium hydroxide, trimethyl hydroxide Methoxyammonium, dimethyldihydroxyethylammonium hydroxide, methyltrihydroxyethylammonium hydroxide, phenyltrimethylammonium hydroxide, phenyltriethylammonium hydroxide, benzyltrimethyl hydroxide Ammonium hydroxide, benzyltriethylammonium hydroxide, dimethylpyrrole hydroxide, dimethylpyridine hydroxide hydrogen, diisopropylimidium oxide file, N-alkylpyridine hydroxide and the like. Representative examples of quaternary scales of chemical formula II (where A = P) can be purified according to the method of the present invention include tetramethyl iron hydroxide, tetraethyl scale, tetrapropyl scale, tetrabutyl hydroxide Scale, trimethylhydroxyethylphosphonium hydroxide, dimethyldihydroxyethyl iron hydroxide, methyltrihydroxyethyl hydroxide scale, phenyltrimethyl iron hydroxide, phenyltriethylphosphonium hydroxide And benzyl trimethyl iron hydroxide. In another specific embodiment, the tertiary hydroxide of trihydroxide that can be recovered or purified according to the method of the present invention can be represented by the following formula: (Please read the winter and _ items on the back first, then this one hundred packs.

Printed by the Consumer Property Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs of the 1T line. R2 I R'-S · OH * I R3 (IV) 11 This paper size applies to China National Standard (CNS) Α4 specifications (210 X 297 mm) 93 Ministry of Economic Affairs Printed by the Intellectual Property Bureau employee consumer cooperative A7 B7 V. Description of the invention (I) where R1, R2 and R3 are each independently an alkyl group containing 1 to about 20 carbon atoms, and a hydroxyalkane containing 2 to about 20 carbon atoms Or alkoxyalkyl, aryl, or hydroxyaryl or R1 and R2 together with S can form a heterocyclic group, provided that the heterocyclic group contains a C = S group and R3 is the second bond. Examples of tertiary phosphonium hydroxide as shown in Chemical Formula IV include trimethylphosphonium hydroxide, triethylphosphonium hydroxide, tripropylphosphonium hydroxide, and the like. The hydroxide gun may be a commercially available product. In addition, hydroxide guns can be prepared from corresponding gun salts, such as corresponding gun halides, carbonates, formate salts, sulfates, and the like. U.S. Patent Nos. 4,917,781 (Sharifian et al.) And 5,286,354 (Bani et al.) Disclose various manufacturing methods, the citations of which are incorporated herein by reference. There are no particular restrictions on how the hydroxide record can be obtained or prepared. The salt recording system is represented by a combination of any of the aforementioned gun cations and salt anions or acid anions. Please refer to any one of the chemical formulae I to IV. The salt recording system is represented by the substitution of OH-anion with salt or acid anion. Salt anions include acetate, halide (fluoride, chloride, bromide, and iodide), dicarbonate and carbonate, formate, nitrate, phosphate, sulfate, and the like. Prior to contact with the cation exchange material, the solution containing the hydroxide gun and / or gun salt and / or impurities may be concentrated or reprocessed as necessary. That is, the concentration of the hydroxide and / or gun salt in the solution can be increased before contacting with the cation exchange material and / or various impurities can be removed from the gun compound solution. In some embodiments, the solution of the gun and / or gun salt is preferably concentrated before contacting the cation exchange material. The enrichment procedure is known to those skilled in the art, and the procedure includes evaporation, distillation, nanometers _____12 _ — This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) " — (Please read the precautions on the back first, then this page) Installation, 11-wire 501937 A7 B7 V. Description of the invention) Nanofiltration and reverse osmosis. Similarly, these concentration procedures can be used as needed to concentrate the gun salt solution poured into the feed compartment of an electrochemical cell (further explained below). In other embodiments, the gun compound solution is preferably pre-filtered slightly before being contacted with the cation exchange material. Various types of filtration can be performed including gravity filtration, microporous filtration, such as nanofiltration, cross filtration 'cartridge filtration, vacuum filtration, and vacuum filtration. It can also carry out related rough filtration and sieve pretreatment. Filter membranes can be made of known materials used to separate solids / liquids, including plastics-such as PTFE, PVDF, PET, nylon, polyethylene and polypropylene, cellulose acetate, nitrocellulose, regenerated cellulose, nitrocellulose -, Including paper such as dust-free paper, various fibers including glass fiber, and various particles including activated carbon, silica, sand and gravel. Alternatively, the pretreatment may include contacting the gun compound solution with various particulate materials, such as activated carbon, so that organic impurities are adsorbed and thus removed from the solution by the particulate material. In some embodiments, one or more than one filtration may be performed Pretreatment, because each kind of filtration pretreatment can remove different kinds of impurities. For example, in a specific embodiment, two types of filtering pretreatments are performed: organic impurities are almost or partially removed by gravity filtration, and metal impurities are increasing the acid and alkali content of the solution, causing the metal to form insoluble hydroxide salts. This facilitates the removal of almost or part of the filtration by another gravity filtration (ie thus the separation of insoluble species). In other specific embodiments, according to the present invention, the gun compound solution is preferably pretreated by a metal treatment method before being contacted with the cation exchange material. Metal pre-treatment _ 13_ This paper size applies to Chinese National Standard (CNS) A4 (2 mm) X 297 mm) (Please read the precautions on the back before this page)

-Easy-Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs ^ 501937 A7 B7 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs V. Description of the invention (ί /) The process is to remove excess metal impurities in the key compound solution. In a specific embodiment, metal pretreatment includes contacting a gun compound solution with a preset ion exchange material to remove metal. The preset ion exchange material is preferably a preset cation exchange material that can selectively distinguish metal cations and gun cations so that at least a part of metal ion impurities in the gun compound solution are adsorbed by the preset ion exchange material. For example, according to the present invention, a pre-set ion exchange material having an affinity for sodium can be used for metal pretreatment to remove sodium from the gun compound solution before contacting the cation exchange material. In another specific embodiment, the 'metal pretreatment includes contacting the compound solution with a metal complex compound. Metal complex compounds are adsorbed, bonded, complexed, covalent, clamped or engaged in at least a portion of the metal ion impurities in the gun compound solution, thereby removing them before contacting the cation exchange material of the present invention. Remove. Examples of metal complexes include crown ethers, cryptands and sweet compounds (diamines, diones, etc.). In yet another embodiment, the metal pretreatment includes contacting the gun compound solution with an insoluble (at least partially insoluble) stimulant @ acid or salt capable of forming contact with the metal cation, thereby contacting the cation exchange material of the present invention Capable of removing sediment from the stomach and thus removing metal from the solution. According to the present invention, the solution containing the recording compound is contacted with the cation exchange material so that the cation exchange material adsorbs the gun cations (derived from the nitrogen oxidation gun and / or gun salt) in the solution. The cation exchange material can be any of a variety of effective ion exchange materials with ion cations derived from gun compounds. The cation exchange material may be a weakly acidic cation exchange material or a strongly acidic cation exchange material. The base material of the cation exchange material can be an organic cation exchange material, for example (please read the precautions on the back first and then the page)-binding line This paper size applies the Chinese National Standard (CNS) A4 specification (21〇χ 297 public celebration) 501937 A7

Stone, silicone or cation exchange resin or inorganic cation exchange material, such as boiling analogs. The cation exchange materials of the Intellectual Property Bureau of the Ministry of Economic Affairs and the Industrial Cooperative Cooperative Society can be powder, nine grains, small grains, films and domain fiber materials. Two _ two perspectives _ good money materials can be combined, such as the combination of acidic cation exchange materials and cation exchange materials, the combination of inorganic cation parent exchange materials and organic cation exchange materials' = species or — 顚 上 each- The cation exchange material group of different forms, such as the end face dimension, depends on the significant characteristics and properties of the gun compound solution. In terms of the addition of the If ion exchange material, the economic viewpoint and the ion exchange capacity are preferably granular weakly acidic cation exchange resins and / or strongly acidic cation exchange resins. Examples of the cation exchange material include a sulphuric acid group or a carboxylic acid group, for example, a styrene polymer or copolymer such as polystyrene and the like, an acrylic polymer such as polyacrylic resin and the like, or Copolymers, such as methacrylic polymers and copolymers such as polymethacrylic resins and the like, and polymers or copolymer matrices of tetrafluoroethylene polymers or copolymers such as polytetrafluoroethylene and the like, Alternatively, a colloidal or porous cationic resin produced by a modified polymer or copolymer matrix prepared by using a crosslinking agent such as divinylbenzene and the like to modify the polymer or copolymer is incorporated. The cation exchange materials further include phosphorus and phosphorous acid resins as well as inorganic cation exchange materials such as zeolites, silicones, and the like. Specific preferred examples include cation exchange resin solids produced by Rohm & Haas Corporation and Dow Chemical Company under the trade names AMBERLITE® and DOWEX®, respectively. More specific examples include Rohm & Haas Corporation's 15 paper sizes applicable to the Chinese National Standard (CNS) A4 (210X 297 mm) (please read the precautions on the back first and then the page). · Tr cable I — 1 3 9 11 ο Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 V. Description of Invention (fj) Products with the name AMBERLITE, such as IR-100, IR-105, IR-105 G, [R-112, IR -120, IR-122, IR-124, IRC-50, IRC-76 and IRC-84SP, and products under the trade name DUOLITE, such as C-280, C291, C-433 and C-464; C-464; Products under the trade name DOWEX, such as HGRW2, HCR-S, HGRW2, MWC-1, 50WX2, 50WX4 and 50WX8, and products under the trade name MONOSPHERE DOWEX of Dow Chemical Company, luxury! J such as C350, C500 and C650; Sybron's Ionac CC and C-267; Organo's various cation exchange resins; and Mitsubish Kasei's products under the trade name DIAION, such as PK216H, PK212, PK228, HPK25, SK-1BS, SK-104, SK- 112, SK-116, WK20, WK40 and WK100. In a preferred embodiment, the cation exchange resin is IRC-84SP from Rohm &Haas; MONOSPHERE DOWEX C350, C500 and C650 from Dow Chemical; and PK216, PK212 and WK40 from Mitsubish Kasei. . Depending on the significant characteristics and form of the cation exchange material, any method of contacting a solution containing a gun and / or gun salt with the cation exchange material may be used. For example, a column system is used when a solution containing a gun compound is continuously passed through a column filled with a cation exchange material, and a cation exchange material is added to the solution containing a gun compound so that the latter is contacted with the former by stirring, and then mixed with A batch system is used in the case of filtration of solids to separate solid and liquid. The acid is then contacted with the cation exchange material in any manner, such that gun cations previously adsorbed by the cation exchange material are flushed out and removed therefrom. In the specific embodiment using the column system, the acid can be added in a countercurrent or countercurrent manner to apply the ti " national standard (2 丨 to ^ public meal)---(Please read the precautions on the back before this Page) Female. Thread 501937 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 ^ __ B7___ 5. Description of the invention (ff) Entry pipe. Because the hydronium ion replaces the gun ion. Therefore, new cation exchange materials can be reused in the present invention. The acid used for the elution step is selected based on the remarkable characteristics of the cation exchange material, the remarkable characteristics of the cations, and the steps related to the electrochemical cell. The acid may be selected from inorganic acids such as hydrochloric acid, hydroboric acid, nitric acid, sulfuric acid, carbonic acid 'phosphoric acid, phosphorous acid and the like, and organic acids such as acetic acid, formic acid, oxalic acid and the like. In a specific embodiment, the pKa of the acid is less than about 5, and the pKa is preferably less than about 4. The acid concentration range is very wide and can be selected from a wide range of more than about 0.01% to more than about 20%. The acid is preferably an inorganic acid. Especially, carbonic acid, hydrochloric acid or diluted sulfuric acid is more preferable, and its concentration exceeds about 0.05% or exceeds about 2.0%. The acid is contacted with the cation exchange material, thereby purifying the gun salt. Gun salts derived from cation-exchange materials are at least partially derived from gun-containing cations (derived from hydroxide and / or gun salts in solution when initially in contact with the cation-exchange material) and anions (from cation-exchange materials). Contact acid derived). The extracted salts include salts composed of gun cations and any of the corresponding acid anions. Specific typical examples include at least one of a hydrogen carbonate gun, a chlorination gun, a bromination gun, a nitric acid gun, a phosphoric acid gun, a formic acid gun, an acetic acid gun, and a sulfuric acid gun, or a salt corresponding to any of the acids described herein. When gun salt is flushed from the cation exchange material, it is best to minimize the amount of acid collected. Although in some embodiments, some acids are usually collected, the amount of acid collected can be minimized by changing the acid flow rate and acid concentration and the gun compound in contact with the cation exchange material. (Please read the precautions on the back first, and then this page)-Binding-The size of the paper is suitable for the Chinese National Standard (CNS) A4 (210X297 mm) 501937 A7 B7 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs Explanation ((f) The best flow rate and concentration are changed according to the salient characteristics of cation exchange materials and gun cations and acids. The flow rate and concentration can be determined by those skilled in the art. A According to the method of the present invention, the hydroxide For example, the above-mentioned hydroxide gun is regenerated (produced, purified, or recovered) in a process including an electrochemical cell. An electrochemical cell may include electrolysis in an electrolytic cell, or electrodialysis in an electrodialysis cell. Electrochemical cells, Generally speaking, it includes at least an anode, a cathode, and an anion-selective film, or an anode, a cathode, a cation-selective film, and a bipolar film. Any one of them may have one or more Units are assembled and operated between cathodes. Many types of unit cells and multiple units are described here. Cells can be used in the electrolytic and electrodialysis cells of the present invention. Multiple unit cells can be composed of many compartments between the anode and cathode, or multiple unit cells can be composed of many compartments including the anode and cathode. Including anodes and cathodes The multi-type unit cell may adopt a unipolar structure or a bipolar structure. There is no particular limitation on the number of unit cells that can be used. However, in a specific embodiment, 'the electrochemical cell of the present invention contains 1 to about 25 Unit cells, preferably from 1 to about 10 unit cells. Unit cells may include at least two or three anode 'cathodes, and at least one anion-selective film, cation-selective film, and bipolar film that can serve as microporous diffusion barriers The compartment 'filter device' may have a controlled pore size or pore size distribution, so that certain ions may or may not pass. Various anion-selective films, cation-selective films, and The bipolar film is described in more detail as follows. The electrochemical cell of the present invention includes Less two compartments or three compartments. Bag (please read the notes on the back first and then this page)-binding and binding This paper size applies to China National Standard (CNS) A4 (210x 297 mm) 501937 A7 B7 5. Description of the invention (A) An electrochemical cell containing at least two compartments usually has a feed compartment and an acid compartment. An electrochemical cell containing at least three compartments usually has a feed compartment and a recycling The compartment and at least one acid compartment and a buffer compartment. Optionally, the electrochemical cell of the present invention may additionally include a passage compartment. In certain embodiments, the electrochemical cell of the present invention may have two compartments. Or, there are two or more compartments, as described above. In other specific embodiments, the electrochemical cell may have two or more compartments. For example, in a specific embodiment Here, the electrochemical cell may have a feed compartment, two buffer compartments, and a recovery compartment. Pour the solution into each compartment. The solution can be based on water, alcohol or glycol as the base, and can be other organic solutions or a combination thereof. In other words, the solution may include water, a mixture of water and an organic liquid, or an organic liquid, where the organic liquid includes alcohols such as methanol and ethanol, ethylene glycol, and the like. In a preferred embodiment, the solution poured into each compartment is an aqueous solution. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. The solution poured into each feed compartment contains gun salt that has been extracted from the cation exchange material. The concentration of gun salt initially poured into the feed compartment is from about 0.01M to about 6M. In a preferred embodiment, the key salt concentration in the solution poured into the feed compartment is from about 0.5M to about 1.5M. In an electrochemical cell containing two or more feed compartments, the concentration of gun salt in the solution poured into the feed compartments in each feed compartment can be the same or different. The feed compartment, as the name suggests, originally contained a gun salt solution containing gun cations, which gun cations were derived from a solution initially contacted with the cation exchange material to be treated with the present invention. In some embodiments, the purified hydroxide gun is recovered from the feed compartment. For example, in the specific embodiment of the electrochemical paper sheet containing only one anion-selective film, the Chinese National Standard (CNS) A4 specification (21 χ 297) is applied. 501937 A7 B7 5. Description of the invention) The purified hydroxide is recovered from the feed compartment (consisting of an anion-selective membrane and cathode) after an electric current is applied. Similarly, in a specific embodiment of an electrochemical cell comprising an anion-selective film and first and second bipolar films, a purified hydroxide gun is applied from a feed cell (selected by anions) after an electric current is applied. Film and one of the bipolar films). The recovery compartment-if present-is initially filled with a solution and is filled with an aqueous solution. The solution poured into the recovery compartment may or may not contain ionic compounds. Ionic compounds are chemical compounds that are partially or fully ionized in a solution, such as an electrolyte. Examples of the ionic compound include salts, metal salts and acids or any compound which forms anions and cations when placed in water. In a preferred embodiment, the ionic compound is the same as the gun salt poured into the feed compartment (or the same as the hydroxide gun recovered from the recovery compartment). In another specific embodiment, the ionic compound is different from the gun salt poured into the feed compartment. After the current passes through the electrochemical cell, the oxidizing gun can be recycled or obtained from the recovery compartment at a certain concentration. In a specific embodiment, the concentration of the recycling Gregory hydroxide gun is more than about 0.5M. In yet another specific embodiment, the concentration of the recovering intergrid hydroxide gun is more than about 1M. In yet another specific embodiment, the concentration of the recovered Glycol hydroxide is more than about 2M. These figures can be used in a specific embodiment where no compartment is recovered in the electrochemical cell when the hydroxide gun is recovered from the feed compartment. In an electrochemical cell containing two or more recovery compartments, the concentration of the organic hydroxide in the solution recovered from the recovery compartments in each recovery compartment may be the same or different. Buffer compartment-if present · 20% of ionic compounds containing a certain concentration of ionic compounds This paper size applies Chinese National Standard (CNS) A4 specifications (210X 297 mm) (Please read the precautions on the back before this page). Τ Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 3 9 11 ο A7 B7 ___ V. Description of the invention (/ (f) liquid. The buffer compartment containing ionic compounds is used to maintain conductivity and reduce the operating battery voltage. Pour into The concentration of the ionic compound in the buffer compartment solution is about 0.1M to about 5M. In a preferred embodiment, the concentration is about 0.5M to about 2M. In the preferred embodiment, the concentration is about 0.7M to Approximately 1.5M. In an electrochemical cell containing two or more buffer compartments, the concentration of ionic compounds in the solution poured into the buffer compartments in each buffer compartment can be the same or different. Via compartments-if present • Fill solution and preferably aqueous solution from the beginning. The solution poured into the compartment may or may not contain ionic compounds. Ionic compounds-if present-are compatible with the buffer compartment The sub-compounds are the same. In most specific embodiments, the compartment system is composed of two cation exchange membranes. After the current passes through the electrochemical cell, gun cations are passed through the compartment in the specific embodiment. Because most of the unwanted impurities do not pass through the compartment, the compartment is used to further purify the obtained hydroxide gun. The acid compartment is a filling solution and is more preferably an aqueous solution. Poured into the acid compartment The solution may or may not contain ionic compounds. The ionic compound, if present, may be the same as the ionic compound in the buffer compartment. The concentration of the ionic compound in the solution poured into the acid compartment is from about 0.1M to about 6M. In the specific embodiment, the concentration is about 0.2M to about 3M. In the preferred embodiment, the concentration is about 0.5M to about 1.5M. After the current passes through the electrochemical cell, the key cations move toward the cathode, and the gun salt is From the feed compartment to the acid compartment. After the solution containing the hydroxide gun and / or gun salt is contacted with the cation exchange material, the acid can be recovered from the acid compartment Reuse, especially in continuous operation, as ______------ 2J ___- This paper size is applicable to China National Standard (CNS) A4 specification (210χ 297 & ϋ --------- 装 _I (Please read the notes on the back first to save this tribute) Printed by the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 501937 Printed by the Employees’ Cooperative of the Intellectual Property Bureau of the Ministry of Economy A7 _____ B7 V. Description of the invention (for contact with cation exchange materials Some specific embodiments of the electrochemical cell that can be used in the present invention will be described with reference to the drawings as follows. Although a specific embodiment of a different electrochemical cell is described with the drawings here, those skilled in the art will It is understood that other specific embodiments not specifically described in the drawings of the present invention are also within the spirit of the present invention. FIG. 1 illustrates a specific embodiment of an electrochemical cell. The figure is a perspective view of an electrochemical cell 10. The electrochemical cell 10 includes an anode 11, a cathode 12, and an anion starting from the anode 11. A unit cell of the selective film 13. The electrochemical cell 10 includes two compartments: that is, an acid compartment 14 and a feed compartment 15. When operating the electrochemical cell 10 as shown in the figure, the salt is poured into the feed compartment 15. The ionic compound solution, preferably an ionic compound aqueous solution, is poured into the acid compartment 14. The potential is established and maintained between the anode and the cathode, so that when the gun salt anion is attracted, it moves to the anode and enters the acid compartment 14 through the anion-selective membrane 13 to generate the current of the entire battery. The gun cation is combined with hydroxide ions in the compartment between the feeds to produce the desired hydroxide gun. Impurities may pass through the anion-selective membrane and thus move to the acid compartment. The regenerated hydroxide gun is thus formed and recovered from the feed compartment 15. In a preferred embodiment, the acid can be recovered from the acid compartment 14. FIG. 2 illustrates a specific embodiment of another electrochemical cell. The figure is a low-level view of an electrochemical cell 20. The electrochemical cell 20 includes an anode 21, a cathode 22, and a A unit cell of the anion-selective film 23 and the cation-selective film 24. The electrochemical cell 20 contains Please read the back gutter 22 This paper size applies to China National Standard (CNS) A4 (210X 297 mm)

3 9 1X A7 ___B7_ V. Description of the invention) Three compartments: namely, the acid compartment 25, the feed compartment 26 and the recovery compartment 27. When the electrochemical cell 20 shown in Fig. 2 is operated, gun salt is poured into the feed compartment 26. The ionic compound solution, preferably the ionic compound aqueous solution, is poured into the acid compartment 25 and the recovery compartment 27. The potential is established and maintained between the anode and the cathode to generate the current of the entire battery when the gun salt anion is attracted to the anode and moves through the anion-selective membrane 23 into the acid compartment 25. The gun cation is attracted to the cathode and passes through the cation-selective film 24 into the recovery compartment of the desired hydroxide gun which is combined with the hydroxide ion. The impurities are not attracted to the cathode and pass through the anion-selective membrane 23 and / or do not pass through the cation-selective membrane 24 and therefore remain in the feed compartment 26 and / or move to the acid compartment 25. The regenerated hydroxide gun is thus formed and recovered from the recovery compartment 27. In a preferred embodiment, the acid can be recovered from the acid compartment 25. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. Figure 3 illustrates a specific embodiment of another electrochemical cell. This figure is a general view of an electrochemical cell 30. The electrochemical cell 30 includes an anode 31, a cathode 32 And a unit cell including the first bipolar film 33, an anion-selective film 34, and the second bipolar film 35 from the anode 31. The electrochemical cell 30 includes four compartments: that is, a first buffer compartment 36, an acid compartment 37, a feed compartment 38, and a second buffer compartment 39. When operating the electrochemical cell 30 shown in Fig. 3, the salt is poured into the feed compartment 38. The ionic compound solution, preferably the ionic compound aqueous solution, is poured into the acid compartment 37 and the first and second buffer compartments 36 and 39. The potential system is established and maintained between the anode and the cathode, so that when the gun salt anion is attracted, it moves to the anode and enters the acid compartment 37 through the anion-selective membrane 34 to produce the whole ______23 ____ This paper size applies Chinese national standards ( CNS) A4 specification (210X 297 mm) 93 A7 B7 printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs V. Invention description (v \) The battery current. Gun cations remain in the feed compartment of the hydroxide gun that combines with hydroxide ions formed on the anode side of the bipolar film to produce the desired hydroxide gun. Impurities may pass through the anion-selective film 34. The regenerated hydroxide is formed and recovered from the feed compartment 38. In a preferred embodiment, the acid can be recovered from the acid compartment 37. FIG. 4 illustrates a specific embodiment of another electrochemical cell. The figure is a perspective view of the electrochemical cell 40. The electrochemical cell 40 includes an anode 41, a cathode 42, and A unit cell of a bipolar film 43 and a cation-selective film 44. The electrochemical cell 40 includes three compartments: that is, a buffer compartment 45, a feed compartment 46, and a recovery compartment 47. When operating the electrochemical cell 40 as shown in Fig. 4, the salt is poured into the feed compartment 46. The ionic compound solution, preferably the ionic compound aqueous solution, is poured into the buffer compartment 45 and the recovery compartment 47. The potential system is established and maintained between the anode and the cathode while the gun salt remains in the feed cell 46. The gun ions are attracted by gravity to the cathode and pass through the cation-selective film 44 to enter the recovery compartment 47 of the desired hydroxide gun by combining with hydroxide ions formed on the surface of the cathode. The impurities are not attracted to the cathode and / or do not pass through the cation-selective membrane 44 and therefore remain in the feed compartment 46. The regenerated hydroxide gun is thus formed and recovered from the recovery compartment 47. In a preferred embodiment, the acid can be recovered from the feed compartment 46. FIG. 5 illustrates a specific embodiment of another electrochemical cell. The figure is a perspective view of the electrochemical cell 50. The electrochemical cell 50 includes an anode 51, a cathode 52, and A unit cell of a bipolar film 53, a cation-selective film 54 and a second bipolar film 55. ___24 _____ This paper size is applicable to China National Standards (CNS) A4 size (210X 297mm) (Please read the precautions on the back before this page) -Packing-, 1 · -Line 3 9 11 Employees of Intellectual Property Bureau, Ministry of Economic Affairs Printed by the consumer cooperative A7 _ B7 V. Description of the invention (vl) The electrochemical cell 50 includes four compartments: namely, the first buffer compartment 56, the feed compartment 57, the recovery compartment 58 and the second buffer compartment. 59. When the electrochemical cell 50 shown in Fig. 5 is operated, gun salt is poured into the feed compartment 57. The ionic compound solution, preferably the ionic compound aqueous solution, is poured into the recovery compartment 58 and the first and second buffer compartments 56 and 59. The potential is established and maintained between the anode and the cathode to generate the entire battery current while the gun salt is retained in the feed compartment 57. Key cations are attracted to the cathode and pass through the cation-selective film 54 into the recovery compartment 58. In the recovery compartment 58, gun cations are combined with hydroxide ions formed on the anode surface of the second bipolar film 55. To produce the desired hydroxide gun. The impurities are not attracted to the cathode and / or do not pass through the cation-selective membrane 54 and therefore remain in the feed compartment 57. The regenerated hydroxide gun is thus formed and recovered from the recovery compartment 58. In a preferred embodiment, the acid can be recovered from the feed compartment 57. 'Figure 6 illustrates a specific embodiment of another electrochemical cell. This figure is a perspective view of an electrochemical cell 60. The electrochemical cell 60 includes an anode 61, a cathode 62, and A unit cell of a bipolar film 63, an anion-selective film 64 and a cation-selective film 65. The electrochemical cell 60 includes four compartments: that is, a buffer compartment 66, an acid compartment 67, a feed compartment 68, and a recovery compartment 69. When the electrochemical cell 60 shown in Fig. 6 is operated, the salt is poured into the feed compartment 68. The ionic compound solution, preferably the ionic compound aqueous solution, is poured into buffer compartment 66, acid compartment 67 and recovery compartment 29. The potential system is established and maintained between the anode and the cathode, so that the anions of the key salt are attracted and moved to ___25__ This paper size applies to the Chinese National Standard (CNS) A4 specification (210X 297 mm) (Please read the note on the back first Matters are repeated)-Binding-501937 A7 V. Description of the invention (> Aj) The anode and the anion-selective membrane 64 enter the acid compartment 67 to generate the current of the entire battery. The gun cation is attracted to the cathode and passes through the cation-selective film 65 into the recovery compartment 69 of the desired hydroxide gun which is combined with the hydroxide ion. Impurities move to the cathode without being attracted by passing through the anion-selective membrane 64 and / or without passing through the cation-selective membrane 65 and therefore remain in the feed compartment 68 and / or move to the acid compartment 67. The regenerated hydroxide gun is thus formed and recovered from the recovery compartment 69. In a preferred embodiment, the acid can be recovered from the acid compartment 67. FIG. 7 illustrates a specific embodiment of another electrochemical cell. The figure is a perspective view of an electrochemical cell 70. The electrochemical cell 70 includes an anode 71, a cathode 72, and A unit cell of a bipolar film 73, an anion-selective film 74, a cation-selective film 75, and a second bipolar film 76. The electrochemical cell 70 includes five compartments, that is, a first buffer compartment 77, an acid compartment 78, a feed compartment 79, a recovery compartment 80, and a second buffer compartment 81. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. When operating the electrochemical cell 70 shown in Figure 7, pour the salt into the feed compartment 79. The ionic compound solution, preferably the ionic compound aqueous solution, is poured into the first and second buffer compartments 77 and 81, the acid compartment 78 and the recovery compartment 80. The potential system is established and maintained between the anode and the cathode to generate an electric current for the entire battery when the gun salt anion is attracted to the anode and moves through the anion-selective membrane 74 into the acid compartment 78. The gun cation is attracted to the negative electrode and enters the recovery compartment 80 through the cation-selective membrane 75. In the recovery compartment 80, the gun cation is combined with the hydroxide ion to generate the desired hydroxide gun. Impurities move to the cathode without being attracted by gravity. The anion-selective thin paper size applies the Chinese National Standard (CNS) A4 specification (210X 297 mm). 501937 A7 B7 Intellectual Property Bureau of the Ministry of Economic Affairs. Explanation (4) Membrane 74, and / or did not pass through the cation-selective membrane 75 'and therefore remained in the feed compartment 79 and / or moved to the acid compartment 78 °. The regenerated hydroxide was thus formed and recovered from the compartment. 80 recycling. In a preferred embodiment, the 'acid can be recovered from the acid compartment 78. Figure 8 illustrates a specific embodiment of another electrochemical cell, which is a perspective view of the electrochemical cell 90, the electrochemical The battery 90 includes an anode 91 ′, a cathode 92, and a first cation selective film 93, a first bipolar film 94, and a first anion selective film 95 ′. A unit cell of the second bipolar film 97, the second anion selective film 98, the third cation selective film 99, and the fourth cation selective film 100. The electrochemical cell 90 includes nine compartments: That is, the first buffer compartment 101, the second buffer compartment 102, the first acid compartment 103, the first feed compartment 104, the first recovery compartment 105, the second acid compartment 106, and the second feed Compartment 107, second recovery compartment 108, and third buffer compartment 109. When operating the electrochemical cell 90 as shown in Figure 8, pour salt into the first and second feed compartments 104 and 107 The ionic compound solution, preferably the ionic compound aqueous solution is poured into the first, second and third buffer compartments 101, 102 and 103, the first and second acid compartments 103 and 106, and the first and second recovery Cells 105 and 108. The potential system is established and maintained between the anode and the cathode so that the gun salt anion is attracted to the anode and moves through the first and / or second anion selective membranes 95 and 98 into the first and / Or the second acid compartments 103 and 106 generate the current of the entire battery. The gun cation is attracted to the cathode and enters the first and 27 through the second and / or third cation selective membranes 96 and 99. Please read the back φ Precautions

The page size of this paper applies the Chinese National Standard (CNS) A4 specification (210X 297 mm) 501937 A7 ------_ B7___ 5. Description of the invention (vp ^ / or the first recycling compartment 105 and i〇8, In the first and / or second recovery compartments 105 and 108, the _ cation is combined with the hydroxide ion to produce the desired hydroxide record. The impurities move to the cathode without being attracted by the first and / or second anion The selective membranes 95 and 98, and / or do not pass through the second and / or third cationic selective membranes 96 and 99, and therefore remain in the first and / or second feed compartments 104 and 107 and / or move to The first and / or second acid compartments 103 and 106. Regenerated hydroxide records are thus formed and recovered from the first and / or second recovery compartments 105 and 108. In a preferred embodiment Here, the acid can be recovered from the first and / or second acid compartments 103 and 106. The method of the present invention can be operated continuously or batchwise. In a continuous method, the acid recovered from an electrochemical cell can be reacted with a cation The exchange material is in contact with the lance gun salt. The operation of the method of the present invention is generally continuous and continuous recovery cycle. A component. It is recycled by pumping and / or gas release. It is printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. Various materials can be used as anodes in electrochemical cells. For example, the anode can be made of metal. For example, titanium-plated electrodes, tantalum, nickel, zirconium, or alloys thereof. Generally, the anode has an impenetrable and catalytic film, which may include metallic precious metals, such as platinum, iridium, rhodium or an alloy thereof, or contain A mixture of oxides or precious metals (such as ferrite, copper, nails, or screws), a conductive oxide mixture of at least one of the mixed oxides. In a specific embodiment, the anode is a spatially stable anode, such as titanium Anode with ruthenium oxide and / or iridium oxide as the substrate. In a preferred embodiment, the anode is a space-stable anode with titanium as the substrate and ruthenium oxide on it. Has been used Various materials used as anodes in electrochemical cells can be included in the batteries used in the above and other specific embodiments of the present invention. Cathode Material Half Bucket 28 — This Paper Ruler Applicable to China National Standard (CNS) A4 specification (210X 297 mm) ~~ '~~ 501937 A7 B7_ ____ 5. Description of the invention (lA) Series includes nickel, iron, stainless steel, nickel-plated titanium, graphite, carbon steel (iron ) Or its alloys, etc. "alloys, which refers to a wide range, includes very intimate mixtures of two or more metals and includes a metal plated on another metal. The electrochemical method used in the method of the present invention The battery system includes at least one ion-selective film, and in some embodiments, includes at least one bipolar film. The grid system is defined as an ion-selective film and / or a bipolar film and / or one or more anodes and / Or an area between two or more of the one or more cathodes. Ion-selective membranes and / or bipolar membranes act as diffusion barriers and / or gas separators. The cation-selective film used for the method and battery of the present invention printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economics may be any cation-selective film that has been used for electrochemical purification or recovery of a recycling hydroxide gun. Preferably, the cation-selective film should include a material with a long service life, such as a film based on a fluorocarbon series, or an inexpensive material from a polystyrene or polypropylene series. However, preferably, the cation-selective film usable in the present invention includes a cation-selective group, such as perfluorosulfonic acid and perfluorosulfonic acid / perfluorocarboxylic acid, and a perfluorocarbon polymer film (such as EI dupont Nemours & Co., the "Nafion" series of fluorinated films (such as DuPont's Cationic Nafion 902 film). Other suitable cation-selective films include CMV cation-selective films (produced by Asahi Glass) and styrene divinylbenzene copolymer films containing cation-selective groups such as sulfonate groups, carboxylate groups, and the like. Raipore Cationic R1010 (from Pall RAI), and NEOSEPTA CMH and NEOSEPTA CMI films (from Tokuyama Soda) are particularly suitable for use with higher molecular weight quaternary compounds. The preparation and structure of the cation-selective membrane is described in the heading "Membrane Technology ----- 29 _ This paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X 297 mm) 3 9 1X ο A7 __________B7__________ V. Invention Description)-Encyclopedia of Chemical Technology, Kirk-Othmer, Third Edition, Vol. 15, pp. 92-131, Wiley & Sony, NY., 1985-. The various cationic selective membranes described in these pages that can be used in the method of the present invention are incorporated herein by reference. It is preferable to use at least one cation selective film in the electrochemical cell. Any type of anion-selective film can be used, including a film used in a method for desalting slightly alkaline water. Preferably, the film should be selective for specific anions (such as halide ions) present in the battery. Anion-selective membranes are described in the document entitled "Membrane Technology" -Encyclopedia of Chemical Technology, Kkk-Othmer, Third Edition, Vol. 15, pp. 92-131, Wiley & Sony, NY, 1985-. The various anion-selective films described in these pages that can be used in the method of the present invention are incorporated herein by reference. The anion-selective films that can be used in electrochemical cells and are commercially available are as follows: AMFLON series 310 (has been Fluorinated polymer substituted with quaternary amine group as matrix, produced by American Machine & Foundry Company) Printed by the Consumer Cooperative of Intellectual Property Bureau, Ministry of Economic Affairs; IONAC ΜΑ 3148, Μ 3236 and Μ 3475 (has been replaced by quaternary ammonium Polymer as matrix, derived from heterophasic polyvinyl chloride, manufactured by Ritter-Pfaulder of the Permutit Division; Tosflex IE-SF 34 or IE-SA 48 (manufactured by Tosoh, a Stable film in the medium); NEOSEPTA AMH, NEOSEPTA ACM, NEOSEPTA AFN or NEOSEPTA ACLE-SP (manufactured by Tokuyama Soda): and Selemion ASV, Selemi on AMV and Selemion AAV (manufactured by Asahi Glass). In a specific embodiment, Tosflex IE-SF 34 and NEOSEPTA AMH anion exchange film are better, because its _30 paper size is applicable to China National Standard (CNS) A4 specifications (210X297 mm) 501937 A7 __ B7 __ V. Description of the invention (&f;) Stable in alkaline solution, for example, the hydroxide-containing solution related to the method of the present invention. Bipolar film used in electrochemical cells contains three Composite film of two parts: a cation-selective side or region, an anion-selective side or region, and an interface between two regions. When the direct current passes through the bipolar film toward the cation-selective side or facing the cathode, it is affected by the electric field. The H + and OH · ions obtained by hydrolysis are transferred to obtain electrical conduction. Bipolar films are described in, for example, US Patent 2,829,095, 4,024,043 (single film type bipolar film) and US Patent 4,116,889 (mold bipolar film) ). Bipolar films that can be used in the present invention include NEOSEPTA BIPOLAR 1 (produced by Tokuyama Soda), WSI BIPOLAR and Analytics Bipolar Film. The steps involved in electrochemical cells are performed by applying an electrical current (usually a direct current) between the anode and the cathode. The current through electrochemical electricity is a current determined by the design and performance of the battery, which can be easily understood by those skilled in the art and / or can be determined by regular experiments. The current density may be about 10 to about 500 microamperes per square centimeter, and a current density of about 70 to about 300 microamperes per square centimeter is more preferred. Higher or lower current densities can be used for a specific purpose. The current density is applied to the battery for a period of time sufficient to regenerate or form the required number of hydroxide guns in the feed compartment or recovery compartment. During the steps related to an electrochemical cell, it is usually best to maintain the temperature of the liquid inside the cell at about 2 ° C to about 90 ° C, preferably at about 20 ° C to about 60 ° C. Also during the steps related to electrochemical cells, it is usually preferred that the liquid acid and alkali in the battery is either alkaline or acidic. This can be done by _3J____ this paper. The dimensions apply to the Chinese National Standard (CNS) A4 specification (210X 297 mm) ~ '

(Please read the precautions below and fill in I__ Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs

Claims (1)

501937 A8B8C8D8 + 0Η · Recycling compartment recycling on the cathode side of the sub-selective film for patent application ° 6. Method according to item 1 of the patent application scope 'wherein the electrochemical cell includes at least five compartments, one cathode, one anode In the order from anode to cathode, it also contains a first bipolar film, an anion-selective film, a cation-selective film, and a second bipolar film. The feed compartment is formed by the film, and the hydroxide gun is recovered from the recycle compartment formed by the cation-selective film and the second bipolar film. 7. The method according to item 6 of the application, wherein the acid is recovered from the acid compartment formed by the first bipolar film and the anion-selective film. 8. The method according to item 1 of the scope of patent application, wherein the hydroxide gun includes a four-stage ammonium hydroxide represented by the following formula: ^ R2, IR, N-R3 I R4 where each of R1, R2, R3, and R4 is independently An alkyl, aryl, or R1 and R2 group containing 1 to about 10 carbon atoms together is an alkyl group that forms an aromatic or non-aromatic heterocyclic ring with N, provided that if the heterocyclic group contains a C = N, then R3 Is the second key. 9. The method according to item 1 of the scope of patent application, which further includes applying the Chinese National Standard (CNS) A4 specification (210 X 297 mm) to this paper size (please read the precautions on the back before writing this page) 501937 ei D8 6. Scope of patent application Silk salt concentration formed adjacently and in the feed compartment on the anode side of the cation-selective film. 10. The method according to item 9 of the scope of patent application, wherein the gun salt concentration is performed by one of reverse osmosis, distillation, nanofiltration, and evaporation. 11. A method of recovering a lance from a solution containing a key compound, comprising: (A) contacting the solution with a cation exchange material such that at least a portion of the lance from the recorded compound is adsorbed by the cation exchange material; ( B) contact the acid with the cation exchange material to extract gun salt; (C) pour the gun salt into a cell comprising at least two compartments, a cathode and an anode, and an anion-selective film disposed therein, and an electric current flows through the battery An electrochemical cell by which a hydroxide gun is regenerated; and (D) recovering the hydroxide gun from the battery, wherein the solution containing the quaternary ammonium compound further contains impurities, the method further comprising pre-treating the quaternary ammonium containing quaternary ammonium before performing step (A) A solution of compounds and impurities to remove at least a portion of the impurities. 12. The method according to item 11 of the scope of patent application, wherein the gun salt is poured into the feed compartment formed adjacently and on the cathode side of the anion-selective film, and the hydroxide gun is recovered from the feed compartment, and The acid is desirably recovered from an acid compartment formed adjacently and on the anode side of the anion-selective film. 13. The method according to item 11 of the scope of patent application, wherein the extracted salt system in step (b) includes at least one of hydrogen chloride record, chloride record, bromide record, nitric acid record, and sulfuric acid gun. 3 scales are applicable to China National Standard (CNS) A4 specifications (210 X 297 mm) ^ ~ (Please read the precautions on the back before writing this page), 1T- · line 501937 A8B8C8S 6. Application scope of patents 14 · According to the application The method of item 11 of the patent, wherein the hydroxide includes quaternary ammonium hydroxide, quaternary hydroxide scale or quaternary hydroxide. 15. The method according to item 11 of the scope of patent application, wherein the electrochemical cell includes at least three compartments, a cathode, an anode, and an order from the anode to the cathode, further comprising an anion-selective film and a cation-selectivity In the film, gun salt is poured into a feed compartment formed by an anion-selective film and a cation-selective film, and the hydroxide gun is recovered from a recovery compartment formed adjacently and on the cathode side of the cation-selective film. 16. The method according to item 11 of the scope of patent application, wherein the electrochemical cell includes at least four compartments, a cathode, an anode, and in order to ensure that from the anode to the cathode, it further includes a first bipolar film and an anion-selective film. , And the second bipolar film, the gun salt is poured into the feed compartment formed by the anion-selective membrane and the second bipolar membrane, and the hydroxide gun is recovered from the feed compartment. Π · The method according to item 16 of the scope of application, wherein the acid is recovered from the acid compartment formed by the first bipolar film and the anion-selective film. 18. The method according to item 11 of the scope of patent application, in which the hydroxide gun includes a four-stage hydroxide mirror shown in the following formula ... -3 -2 I 4 R IN IR • ί + H (CNS) A4 size (210 X 297 mm) (Please read the precautions on the back before writing this page) 501937 B8 C8 D8 6. Scope of patent application (please read the notes on the back before filling this page) where R1, R2, R3 and R4 are each independently an alkyl group, aryl group containing 1 to about 10 carbon atoms, or R1 and R2 are the radicals that together form an aromatic or non-aromatic fluorene ring with N, provided that if the heterocyclic group contains a C == N, then R3 is the second bond. 19. The method according to item 11 of the scope of patent application, further comprising concentrating gun salt in a feed compartment formed adjacently and on the anode side of the cation selective film. 20. The method according to item 19 of the scope of patent application, wherein the gun salt concentration is performed by one of reverse osmosis, distillation, nanometer filtration and evaporation. 21. · A method of recovering quaternary ammonium hydroxide from a solution containing a quaternary ammonium compound, comprising: (A) contacting the solution with a cation exchange material such that at least a portion of the quaternary ammonium from the quaternary ammonium compound The cations are adsorbed by the cation exchange material; (B) the inorganic acid is contacted with the cation exchange material to extract the quaternary ammonium salt; line (C) pours the quaternary ammonium salt into at least four compartments, a cathode and an anode, In the order from anode to cathode, an electrochemical cell including a bipolar film, an anion-selective film and a cation-selective film, and a current flowing through the battery m to regenerate quaternary ammonium hydroxide; and (D) The quaternary ammonium hydroxide is recovered from the battery, and the solution containing the quaternary ammonium compound also contains impurities. The method further includes pre-treating the solution containing the quaternary ammonium compound and impurities to remove at least a portion of the solution before performing step (A). Portions of impurities. 22. The method according to item 21 of the scope of patent application, in which the quaternary ammonium salt is poured into the feed room formed by an anion-selective film and a cation-selective film. 5 This paper size is applicable to China National Standard (CNS) A4 specification (210 X 297 male) 501937 B8. C8 D8 6. The scope of patent application, and quaternary ammonium hydroxide is recovered from the recovery compartment formed adjacently and on the cathode side of the cation-selective film. 23. The method according to item 21 of the scope of patent application, wherein the gun salt extracted in step (B) includes quaternary ammonium bicarbonate, quaternary ammonium chloride, quaternary ammonium bromide, quaternary ammonium nitrate, and quaternary sulfate At least one of them. 24. The method according to item 21 of the application, wherein the quaternary ammonium hydroxide includes tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, methyl hydroxide Triethylammonium hydroxide, methyltributylammonium hydroxide, methyltripropylammonium hydroxide, and diethyldimethylammonium hydroxide. 25. The method according to item 21 of the patent application, wherein the electrochemical cell includes at least five compartments, a cathode, an anode, and an order from the anode to the cathode, and further includes a first bipolar film, an anion selectivity Film, a cation-selective film and a second bipolar film, the quaternary ammonium salt is poured into the feed compartment formed by the anion-selective film and the cation-selective film, and the quaternary hydroxide is selected from the cation-selective film. The film and the second bipolar film are formed / recycled in the recycling compartment. 26. The method according to item 25 of the application, wherein the inorganic acid is recovered from the acid compartment formed by the first bipolar film and the anion-selective film. 27. The method of claim 21, further comprising concentrating the quaternary ammonium salt in a feed cell formed from an anion-selective film and a cation-selective film. 28. The method according to item 27 of the application, wherein the method of concentrating the quaternary ammonium includes removing the quaternary ammonium salt solution from the feed compartment, passing the quaternary ammonium salt solution through the reverse osmosis unit, and passing the concentrated quaternary ammonium The ammonium salt solution returns to the feed room. 6 This paper size is applicable to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) (Please read the precautions on the back before filling this page).-° line A8B8C8D8 501937 6. Application Patent scope grid. (Please read the precautions on the back before writing this page) 29. —A method for recovering tetramethylammonium hydroxide from a waste solution containing tetramethylammonium compounds, which includes: (A) Exchange the waste solution with cations The resin is contacted so that at least a portion of the tetramethylammonium cations from the tetramethylammonium compound are adsorbed by the resin; (B) the inorganic acid is contacted with the cation exchange resin to extract the tetramethylammonium salt; (C) the tetramethylammonium salt is extracted; The methylammonium salt is poured into a cell containing at least five compartments, a cathode, an anode, and in the order from anode to cathode, and also includes a first bipolar film, an anion-selective film, a cation-selective film, and a second An electrochemical cell in which a bipolar film and a current flows through the battery to regenerate tetramethylammonium hydroxide; and (D) recovering tetramethylammonium hydroxide from the battery, wherein the solution containing the quaternary ammonium compound also contains impurities, the method It further comprises pre-treating the solution containing the quaternary ammonium compound and impurities to remove at least a portion of the impurities before performing step (A). 30. The method according to item 29 of the application, wherein the tetramethylammonium salt is poured into the feed compartment formed by the anion-selective film and the cation-selective film, and the tetramethylammonium hydroxide is selected from the cation Recycling compartment formed by the thin film and the second bipolar film. 31. The method according to item 29 of the application, wherein the method is continuous, and the inorganic acid is recovered from the acid compartment formed by the first bipolar film and the anion-selective film, and the inorganic acid is reused in step (B). 32. The method according to item 29 of the scope of patent application, in which the electrochemical cell 7 paper size is applicable to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) 501937 C8 D8 6. Scope of patent application (please read the back of the first Note for rewriting this page) It includes at least nine compartments, one cathode, one anode, and the order from anode to cathode, and also contains the first cation-selective film, the first bipolar film, and the first anion-selective film. , The second cation-selective film, the second bipolar film, the second anion-selective film, the third cation-selective film, and the fourth cation-selective film. The selective membrane and the second cation-selective membrane, and the feed compartment formed by the second anion-selective membrane and the third cation-selective membrane: and tetramethylammonium hydroxide is obtained from the second cation-selective membrane and The second bipolar film, and the recovery compartment formed by the third cation-selective film and the fourth cation-selective film are recovered. 33. The method according to item 32 of the application, wherein the inorganic acid is formed from at least one acid formed by the first bipolar film and the first anion-selective film, and the second bipolar film and the second anion-selective film. Grid recycling. 34. The method according to item 29 of the application, further comprising concentrating the tetramethylammonium salt in the feed compartment formed by the anion-selective film and the cation-selective film. 8 This paper size applies to China National Standard (CNS) A4 (210 X 297 mm)